JP2999624B2 - Method for preparing organopolysiloxane copolymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] The present invention relates to a process for preparing a siloxane-oxyalkylene copolymer by hydrosilylation of an organohydrogensiloxane and an olefin-substituted polyoxyalkylene in a monocarboxylic acid ester of an alkanediol. Viewed from one aspect, the present invention is a method for preparing an improved siloxane-oxyalkylene copolymer composition. Viewed from another aspect, the present invention is a siloxane-oxyalkylene copolymer suitable as a surfactant in urethane foam applications.

[0002]

BACKGROUND OF THE INVENTION The hydrosilylation reaction between an organohydrogenpolysiloxane and an olefin-substituted polyoxyalkylene reactant increases the solubility of the reactant, facilitates handling of the reactant, or moderates the exothermic reaction. To do
Generally, it is carried out in a low molecular weight volatile hydrocarbon solvent such as benzene, toluene, xylene or isopropanol. Less commonly, this hydrosilylation reaction is described in US Pat. It may be carried out in the absence of a solvent as disclosed in US Pat. No. 3,980,688, or in an oxygen-containing solvent such as an ether, polyether or a low or high molecular weight alcohol.

For example, US Pat. 3,280,16
0 and 3,401,192 in n-butyl ether and 50% of isopropyl alcohol / toluene, respectively.
Discloses the preparation of a copolymer in a / 50 mixture. Suitable solvents for the preparation of the siloxane-oxyalkylene copolymer are described in U.S. Pat. 4,122,0
No. 29 discloses the use of isopropyl alcohol and is disclosed in US Pat. In 3,518,288 the inventor has n
-Teaches the use of propanol / toluene. U.S. Pat. The special solvents used in 4,857,583 are:
It is a saturated polyol containing two or more hydroxyl groups. U.S. Pat. U.S. Pat. It states that it acts as a terminator and has harmful effects.

[0004] Of the above solvents, isopropyl alcohol (IPA) is the most common solvent used.
It is known that IPA makes siloxane and glycol compatible and makes the reaction proceed more easily. However, there are disadvantages of using IPA. The disadvantages are as follows: (1) IPA competes with the vinylated glycol for the SiH sites in the siloxane backbone, acts as a defoamer and destabilizes the surfactant. (2) IPA must be stripped from the reaction product and recovered since it reacts with the isocyanate to effectively reduce its loading. This is time consuming and expensive, (3) IPA is compatible with water, which is harmful in the production of polyurethane foam surfactants; and (4) IPA is flammable;
This creates additional manufacturing problems. In addition, IPA
The surfactant produced by using the method always destroys the performance of the surfactant when stripped again.

Contrary to the teachings of the prior art, the present invention utilizes a monocarboxylic acid ester of an alkanediol solvent having only one hydroxyl group. However, using such solvents does not create the disadvantages that appear when using IPA. The present inventors have discovered that such monocarboxylic ester solvents react only minimally with SiH in the siloxane backbone. The monocarboxylate solvent does not need to be stripped or recovered from the product. In addition, the problem of water contamination is reduced because the monocarboxylic acid ester solvent is not hygroscopic. Further, the monocarboxylic acid ester solvent is not flammable.

[0006]

Accordingly, it is an object of the present invention to provide an improved process for preparing siloxane-oxyalkylene copolymers. It is another object of the present invention to provide a method for preparing a siloxane-oxyalkylene copolymer that is useful in the formulation of urethane foam and contains a monocarboxylic acid ester of an alkanediol solvent. Other objects will be readily apparent to those skilled in the art based on the disclosure set forth herein.

[0007]

SUMMARY OF THE INVENTION These copolymers are prepared by a hydrosilylation reaction between an organohydrogenpolysiloxane and an olefin-substituted polyoxyalkylene in the presence of a monocarboxylic acid ester of an alkanediol.

The method of the present invention comprises the following steps (I) to (V): (I) forming a mixture of the following (A) to (C): (A) having the following average structural formula: organohydrogen _{siloxane: R 3 Si [OSi (CH} 3) 2] a [OSiH (CH 3)] b OSiR 3 ( here, R represents 1 to 10 carbon atoms of aliphatic unsaturation
A has an average value of 1 to 192, b
Has an average value of 1 to 30. ) (B) The following (i) to (ii)
a polyoxyalkylene selected from the group consisting of i)

Embedded image (Where (OCH ₂ CH ₂ ) unit and (OCH ₂ CH
(CH ₃ )) units may be block or random, R ¹ is an alkenyl group, R ² may be any substitution that does not interfere with this process, z takes on a value from 1 to 20,
w takes a value of 1 to 20. ) (C) monocarboxylic phosphate esters of alkanediols; the temperature (II) wherein organohydrogensiloxane does not exceed a temperature which reacts with monocarboxylic acid esters of the alkanediol, heating the mixture in an inert gas; (III) adding a catalytic amount of a noble metal hydrosilylation catalyst to the heated mixture; (IV) maintaining the mixture at a temperature below 130 ° C .; (V) recovering the copolymer.

As mentioned above, the present invention provides a process for preparing organosiloxane copolymers which is particularly useful for preparing rigid polyurethane foams, polyurethane foams exhibiting high resilience flexibility and conventional flexible polyurethane foams. . The method involves the hydrosilylation reaction of an organohydrogenpolysiloxane and an olefin-substituted polyoxyalkylene in the presence of a monocarboxylic acid ester of an alkanediol.

The organohydrogensiloxane used in the present invention for the preparation of said copolymer has the following average formula: R ₃ Si [OSi (CH ₃ ) ₂ ] _a [OSiH (CH ₃ )] _b OSiR ₃ (where R is a group having 1 to 10 carbon atoms without aliphatic unsaturation
A has an average value of 1 to 192, b
Has an average value of 1 to 30. ). These organohydrogensiloxanes can be easily prepared by well-known reactions and are commercially available.

The R group in the above organohydrogensiloxane formula can be any hydrocarbon group which is free of aliphatic unsaturation and has 1 to 10 carbon atoms. For example, R can be an alkyl, cycloalkyl, aryl, alkaryl, or aralkyl group. More specifically, R is methyl, ethyl, propyl, isopropyl, butyl, t-butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, tolyl, xylyl, medityl, t-butyl It may be a phenyl, benzyl, 2-phenylethyl or 2-phenylpropyl group.

The olefin-substituted polyoxyalkylene reactants which can be used in the process of the present invention include the following (i) to (ii)
i) selected from:

Embedded image (Where R ¹ is an alkylene group having 3 to 18 carbon atoms; R ² is any substituent that does not inhibit the hydrosilylation reaction, z is a value of 1 to 20, w is 1 to 20)
Is the value of The ethylene oxide unit and the propylene oxide unit may be distributed in a block shape or a random shape.

In the above formula of polyoxyalkylene,
R ¹ may be any monovalent alkylene group. For example, R
¹ can be an ethylene, propylene, butylene, isobutylene, hexylene, octylene, dodecylene, octadecylene or triaconylene group. Preferably,
R ¹ contains 3 to 18 carbon atoms. Examples of OR ^2, there hydroxy, alkoxy, acyloxy, aryloxy, alkylsilyl, acetyloxy, carboxylic acid esters and isocyanates. Preferably, R ² contains no amine or mercaptan groups.

[0014] Unlike the prior art, the present invention utilizes a monocarboxylic ester of an alkanediol. this is,
It has one hydroxyl group as a solvent when performing the hydrosilylation reaction and does not need to be removed from the reaction mixture, especially when the copolymer reaction product is subsequently used in the preparation of urethane foam. Such monocarboxylic ester solvents having one hydroxyl group are essentially harmless. These solvents react only marginally with the SiH in the siloxane backbone. In addition, these solvents are not hygroscopic, thus reducing the problem of water contamination. Further, the monocarboxylic acid ester solvent is not flammable. An example of a preferred monocarboxylic acid ester is 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, and TEXANOL
(Trademark) Eastman Chemical P
products, Inc. Available from

As mentioned above, the hydrosilylation reaction is carried out in the presence of a noble metal hydrosilylation catalyst.
The hydrosilylation reaction between the organohydrogenpolysiloxane and the olefin-substituted polyoxyalkylene reactant is promoted by using a catalytic amount of a noble metal-containing catalyst. Such catalysts are well known, for example, those comprising platinum, palladium or rhodium. The catalyst is used in a catalytic amount sufficient to promote the hydrosilylation reaction. In practice, the amount of catalyst is generally in the range of 1 to 30 ppm of the noble metal, based on the total mixture of reactants and solvent. Chloroplatinic acid (H ₂ PtCl ₆ .H ₂ O) is particularly preferred. Also, this reaction should be carried out at 85 ° C to 130 ° C.
preferable.

The hydrosilylation reaction may optionally be performed in the presence of a carboxylate, as described above. Preferred carboxylate salts contain two or more carbon atoms, carbon,
It is composed of hydrogen and oxygen. Particularly preferred are monocarboxylates containing 2 to 20 carbon atoms. Concentrations up to about 10,000 ppm can be used. The actual amount will depend in part on the carboxylate used.

The hydrosilylation reaction in the above-mentioned reaction method is carried out, and by using a monocarboxylic acid ester of an alkanediol having one hydroxyl group, one of the reactions can be carried out.
Improvements can be obtained in the above aspects. For example, aspects such as reaction rate, reaction yield, reaction selectivity, reaction molding or processing of a reaction product in application to urethane foam. For example, when using 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, at least 6% by weight of 2,2,4-trimethyl-1,3-pentane, based on the weight of the reactants. It has been found that the use of diol monoisobutyrate and 0.05% by weight of a carboxylate, such as sodium acetate, aids in the handling of the reactants. Of course, if desired, more than 6% by weight of the monocarboxylate ester of the alkanediol can be used, and more than 0.05% by weight of sodium acetate can be used. Generally, from 5 to about 50%, more preferably from about 6 to about 37% by weight of the monocarboxylic acid ester of the alkanediol has been found to give good results.

The organopolysiloxane surfactants prepared by the process of the present invention are extremely useful for preparing rigid polyurethane foams, polyurethane foams having high resilience flexibility and polyurethane foams having ordinary flexibility. It has been found to be an excellent and effective surfactant. The surfactants of the present invention have been found to improve the level of performance of polyurethane foams and avoid the need for solvent removal from the reaction mixture from which the organopolysiloxane was prepared. The surfactant is prepared under the desired environmental conditions because a relatively non-toxic solvent is used and its removal from the reaction mixture is avoided.

When making a polyurethane foam using the surfactants of the present invention, one or more polyether polyols are used to react with the polyisocyanate reactant to form urethane bonds. Such polyether polyols have on average at least two, generally 2.0 to 3.5, hydroxyl groups per molecule, and are composed of carbon, hydrogen and oxygen and also phosphorus, halogen and / or chip. Including compounds containing sulfur. Such polyether polyols are well known in the art and are commercially available.

Organic polyisocyanates useful for preparing polyether polyurethane foams according to the method of the present invention are also well known in the art. This is at least 2
It is an organic compound containing two isocyanate groups, and any such compound or a mixture thereof can be used. Toluene diisocyanate is one of many suitable isocyanates that are used commercially in the preparation of foams.
One.

The urethane foam forming reaction is usually carried out in the presence of a small amount of a catalyst, preferably an amine catalyst, usually a tertiary amine. It is also preferable to include a small amount of metal catalyst in addition to the amine catalyst in the components of the reaction mixture. Such supplementary catalysts are well known to those skilled in the art of producing polyether-based polyurethane foams. For example, useful metal catalysts include organic derivatives of tin, especially tin compounds of carboxylic acids, such as tin octoate, tin oleate, and the like.

Either a small amount of a polyurethane blowing agent such as water in the reaction mixture that generates carbon dioxide upon reaction with the isocyanate in situ, a blowing agent that evaporates due to the heat of the reaction, or both. To form a foam. These methods are well-known in the art.

[0023] The polyether-based polyurethane foam of the present invention may be formed according to any processing technique known in the art. For example, it may be formed by a method also particularly known as a “one-shot” method, that is, a “one-step” method. According to this method, the foam is made by performing the reaction between the polyisocyanate and the polyether polyol simultaneously with the foaming operation. It is sometimes convenient to add a surfactant to the reaction mixture as a premix containing one or more blowing agents, polyether polyols and catalyst components.

It is understood that the relative amounts of the various components of the foam formulation are narrow and not critical. Polyether polyols and polyisocyanates make up the major amount in the foam-forming formulation. The relative amounts of these two components necessary to produce the desired urethane structure of the foam are well known in the art. The blowing agent, catalyst and surfactant are each present in the small amounts required to perform the function of the component. Thus, the blowing agent is present in an amount sufficient to foam the reaction mixture, the catalyst is present in a catalytic amount that is necessary to catalyze the reaction that produces urethane at a reasonable rate, and the surfactant is present in the catalyst. First
It is present in an amount sufficient to provide the desired properties as shown in Tables 〜5.

The polyurethane produced according to the present invention comprises
It can be used in the same field as ordinary flexible polyether polyurethane, polyether polyurethane having high resilience flexibility and rigid polyether polyurethane. For example, the foams of the invention can be advantageously used in the manufacture of: fabric interlayers, furniture, mattresses, laminates, linings, building insulation, floor leveling, cushions, padding, carpet underlays, Packaging, gaskets, sealants, thermal insulation, chair books, absorbent for crude oil leaked to the sea, packaging and filling materials, marine floats, auto parts, cigarette filters, boat hulls, sound insulation, collection work Insulation for shipbuilding (for buoyancy), transport of covered vehicles, refrigeration vehicles, tank trucks, hopper trucks, trucks, trailers, storage tanks,
Holds, pipelines, etc.

[0026]

The equipment and test methods used for the results presented here are as follows:

To determine the breathability of the flexible polyurethane foam, the ingredients specified in the formulation were weighed into a cup and the required amount of toluene diisocyanate was added as soon as possible through a pipette. The sample was mixed and a 149 g sample was transferred from the cup to the bucket. The bucket was placed in a hood at 23 ° C. and 5% relative humidity (RH) to complete foaming of the sample. The bucket was then placed in a furnace controlled at 93 ° C. for 10 minutes. A 2 inch × 2 inch × 1 inch block was cut from the center of the foam and placed in a specimen holder of a urethane foam porosimeter. Activate the meter and power vacuum control
Was set to 60. High range valve (high ran
about 0.5 inch (1.2 g) water with an anemometer.
7 cm) reading. Fine adjustment valve (f
Ine tune valve) about 0.5
It was adjusted to show an inch (1.27 cm) reading. The value that appeared on the airflow meter at cubic feet per minute was reported as breathability.

The thermal conductivity of the rigid polyurethane foam was measured using an Anacon Thermal Conductivity Analyzer (Anacon Thermal).
Conductivity Analyzer) was used for the measurement. The results were reported as K-factors defined by:

(Equation 1)

A 7 inch × 7 inch × 1.5 inch sample was cut from the foam to determine the density of the rigid polyurethane foam. The sample was weighed to the nearest 1000th. Density was calculated as lbs / ft ^3.

To determine the foam height of the rigid polyurethane foam, the foaming ingredients were mixed in a cup as specified in the recipe. Immediately, the cup was mounted in the horizontal part of the L-shaped panel, so that the helicopter of the cup rested on the bottom of the panel. The material was foamed at 23 ± 2 ° C. and 50 ± 4% RH until the foam stopped rising. The sample was left for 10 minutes. This sample was taken out of the mold and measured. The foam height of the vertical legs was measured to the nearest tenth of a millimeter.

To determine the foam height of the high resilience polyurethane foam, the foaming ingredients were mixed in a cup as specified in the recipe. The cup was immediately placed gently in the bucket so that the rim of the cup rested on the bottom of the bucket. This material was foamed at 23 ± 2 ° C. and 50 ± 4% RH until the foam stopped rising. The sample was left for 10 minutes. Place the holder and cup / bucket / foam assembly in a furnace at 93 ± 3 ° C for 20 ±
Placed for 0.5 minutes. The sample was taken out of the furnace and immediately measured with a height measuring instrument. As the foam shrinks during cooling,
It is important that the foam be measured as quickly as possible while hot after removal from the furnace. The height of the foam was measured from the bottom of the cup to the top of the foam with an accuracy of up to 1/10 mm. 2
The average height of three samples was reported.

The invention will be further elucidated in view of the following examples. In the following examples, all parts and percentages are by weight unless otherwise specified.

Example 1 In this example, IPA and 2,2,4-trimethyl- were used to determine the amount of SiH consumed by the solvent.
Two hydrosilylation reactions were performed using 1,3-pentanediol monoisobutyrate as a solvent.

A mixture of 42.3 g of organohydrogensiloxane having the following average formula: Me ₃ SiO (Me ₂ SiO) ₁₅₇ (MeHSiO) ₂₁ SiMe ₃ and 100 g of IPA was prepared. A sample was drawn and the% of SiH was measured. The mixture was heated to 75 ° C. and a solution of H ₂ PtCl ₆ .H ₂ O in IPA was added so that the Pt was 30 ppm. The heat source was removed and the exothermic hydrosilylation reaction was allowed to proceed until no further increase in temperature occurred. Heat was applied to the mixture as needed and the temperature was maintained at 82 ° C. for 30 minutes. The mixture was cooled to room temperature and a sample was withdrawn and measured for% SiH. 2,2,4-trimethyl-1,3 instead of IPA as solvent
This process was repeated with pentanediol monoisobutyrate. However, the temperature is 120 ° instead of 82 ° C.
C.

By reacting the sample with a saturated solution of sodium butoxide in a closed system, the SiH of each solvent system was
The consumption was measured. The released hydrogen was measured by a pressure measurement method. The% SiH consumed was calculated. Table 1 shows the results.

[0036] Table 1 Table 1 Solvent% SiH originally% SiH end consumer 1. Isopropyl alcohol 0.0455 0.00795 83% 2. 2,2,4-trimethyl 0.0500 0.03450 31% 1,3-pentanediol Monoiso Butyrate

The results in Table 1 show that IPA consumed 83% of the available SiH sites in the siloxane backbone while 2,2
It clearly shows that 4-trimethyl-1,3-pentanediol monoisobutyrate consumed only 31%. This demonstrates that 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate has lower competition with vinylated glycol for SiH sites in the siloxane backbone. This data shows that the consumption of SiH depends on the molecular form of the solvent (molecul).
ar geometry). This molecular shape theory (molecular geometry)
(etry theory) is proposed as a means of explaining the unusual results obtained with the solvents of the present invention. However, Applicants do not wish to be bound by any theory or hypothesis as to the mechanism by which the compositions of the present invention actually achieve unusual and unexpected results.

Example 2 This example uses 2,2,4 as a compatibilizer instead of IPA.
-Ease of making siloxane oxyalkylene block copolymer surfactants for stabilizing flexible polyurethane foams using trimethyl-1,3-pentanediol monoisobutyrate.

A polyolefin substituted with an olefin having the following average formula
Lioxyalkylene 165.9 g: CH_Two= CHCH_Two(OCH_TwoCH_Two)₁₈(OCHCH_ThreeC
H_Two)₁₈OC (O) CH _Three, Average formula CH_Two= CHCH_Two(OCH_TwoCH_Two)₁₂OC (O)
CH_ThreePolyoxyalkylene substituted with olefin
29.9 g, average formula Me_ThreeSiO (Me_TwoSiO)₁₅₇
(MeHSiO)_{twenty one}SiMe_ThreeOrgano hydrogen white with
56.5 g of xane and 2,2,4-trimethyl-1,3
-147.6 g of pentanediol monoisobutyrate
Got ready. The mixture is degassed by vacuum and blowing nitrogen.
And heated to 75 ° C. H in IPA_TwoPtCl₆・ H
_TwoA solution of O was added so that Pt became 11 ppm. Heat source
And exothermic hydrolysis until temperature rise is no longer observed.
The silylation reaction was allowed to proceed. The temperature of the mixture is 95-11
Heat was applied as needed to keep at 5 ° C. for 30 minutes.

After cooling, ordinary flexible polyurethane foams were evaluated for surfactants. Table 2 shows the results.

[0041] Table 2 Table 2 Solvent foam height (mm) breathable (cfm) 1. 2,2,4-trimethyl 235.4 6.7 1,3-pentanediol mono-isobutyrate 2. Isopropyl alcohol 232.3 6.2

The results in Table 2 show that the foam height and air permeability of a flexible polyurethane foam using 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate as a surfactant solvent were measured at the interface. It shows that it surpasses IPA as an activator.

Example 3 Average Formula CH ₂ ＣＨCHCH ₂ (OCH ₂ CH ₂ ) ₁₈ (OCHC
234.3 g of polyoxyalkylene substituted with an olefin having H ₃ CH ₂ ) ₁₈ OC (O) CH ₃ , average formula Me ₃
SiO (Me ₂ SiO) ₁₀₃ (MeHSiO) ₁₀ SiMe
65.7 g of an organohydrogensiloxane having ₃ and 2,
25.0 g of 2,4-trimethyl-1,3-pentanediol monoisobutyrate was prepared. The mixture was degassed by vacuum and blowing of nitrogen gas and heated to 75 ° C. A solution of H ₂ PtCl ₆ .H ₂ O in IPA was added to a Pt concentration of 11 ppm. Excluding the heat source, the exothermic hydrosilylation reaction was allowed to proceed until no temperature increase was observed. Heat was applied to the mixture as needed to maintain the temperature of the mixture at 95 ° C. for 30 minutes. This process was repeated. However, the temperature was maintained at 115 ° C. for 30 minutes instead of 95 ° C. A third iteration of this process was performed. At that time, the solvent (2,2,4-trimethyl-1,3-pentanediol monoisobutyrate) was not added, and the temperature was maintained at 115 ° C. for 30 minutes.

After cooling, these surfactants were evaluated on ordinary flexible polyurethane foams. Table 3 shows the results.

[Table 3] Table 3 Solvent holding temperature Test amount Height Air permeability (℃) (g) (mm) (cfm) Yes 95 0.52 Flattened No Yes 115 0.52 230.7 7.45 None 115 0.52 221.2 None

The results in Table 3 show that temperatures above 95 ° C. and some compatibilizing solvent are required to make a surfactant that properly stabilizes the polyurethane foam with normal flexibility. Is shown.

Example 4 This example demonstrates the use of siloxane oxy used to stabilize rigid polyurethane foams using 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate instead of IPA as solvent. Explain that an alkylene block copolymer surfactant can be easily prepared.

Average formula CH ₂ ＣＨCHCH ₂ (OCH ₂ CH ₂ )
206.4 g of polyoxyalkylene substituted with an olefin having ₁₂ OH, average formula Me ₃ SiO (Me ₂ Si
₉ ) g of an organosiloxane having O) ₉ (MeHSiO) ₉ SiMe ₃ , 2,2,4-trimethyl-1,3-
30.0 g of pentanediol monoisobutyrate and 0.1 g of sodium acetate were prepared. The mixture was degassed by vacuum and blowing nitrogen and heated to 75 ° C. To this, a H ₂ PtCl ₆ .H ₂ O solution in IPA was added,
It was added to 3 ppm. Excluding the heat source, the exothermic hydrosilylation reaction was allowed to proceed until no temperature increase was observed. Heat the mixture to 120 ° C if necessary
For 30 minutes. This process was repeated using IPA as the solvent.

After cooling, the rigid polyurethane foam was evaluated for these surfactants. Table 4 shows the results.

[Table 4] Table 4 Solvent Thermal conductivity Density Bubble height (K-coefficient) (lbs / ft ³ ) (mm) 1. 2,2,4-trimethyl 0.117 2.41 633.6 -1,3-pentanediol monoisobutyrate 2. Isopropyl alcohol 0.125 2.50 630.0

The results in Table 4 show that 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate has a higher thermal conductivity and density than foams prepared using IPA as a solvent. It shows that it is excellent. It is considered by those skilled in the art that a difference of 0.003 is a significant difference. And in this case, the difference of the K-coefficient is 0.008 unit.

Example 5 This example demonstrates the use of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate as a solvent in place of polypropylene glycol to stabilize a highly resilient, flexible polyurethane foam. The fact that the siloxaneoxyalkylene block copolymer surfactant used to make the surfactant can be easily prepared will be explained.

The average formula CH ₂ ＣＨCHCH ₂ (OCHCH ₃ C
H ₂ ) _2.5 109.5 g of polyoxyalkylene substituted with an olefin having OCH ₃ , average formula Me ₃ SiO (M
e ₂ SiO) (MeHSiO) organosiloxane 115.5g with SiMe _3, 2,2,4-trimethyl -
1,3-pentanediol monoisobutyrate and 0.3 g of sodium acetate were prepared. The mixture was degassed by vacuum and nitrogen gas blowing and heated to 75 ° C.
To this, a solution of H ₂ PtCl ₆ .H ₂ O in IPA was added to Pt.
It was added to a concentration of 14 ppm. Remove the heat source,
The exothermic hydrosilylation reaction was allowed to proceed until no further increase in temperature was observed. Heat was then applied to the mixture as needed and the temperature was maintained at 120 ° C. for 60 minutes. This process was repeated using polypropylene glycol as the solvent.

These surfactants were evaluated using a foam having high resilience and flexibility after cooling. Table 5 shows the results.

[0055] [Table 5] Table 5 Solvent foam height (mm) 1. 2,2,4-trimethyl-361.0-1,3-pentanediol mono-isobutyrate 2. Polypropylene glycol 361.2

The results in Table 5 show that 2,2,4-
It has been shown that surfactants prepared using trimethyl-1,3-pentanediol monoisobutyrate are comparable to surfactants prepared using polypropylene glycol as a solvent.

From the discussion of this specification or the practice of the invention disclosed herein, other embodiments will be apparent to those skilled in the art. The detailed description and examples of the invention are to be regarded as illustrative only, with the true scope and spirit of the invention being indicated by the following claims.

[0058]

The reaction solvent used in the method of the present invention reacts only with a minimal amount of SiH in the siloxane main chain as a reactant, and it does not need to be stripped or recovered from the reaction product, and it has a hygroscopic property. Not flammable.

────────────────────────────────────────────────── (5) References JP-A-60-156733 (JP, A) JP-A-64-87633 (JP, A) JP-A-57-149290 (JP, A) US Patent 4804737 (US) , A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 77/06 C08G 77/12 C08G 77/46

Claims (2)

(57) [Claims] 1. A process for the preparation of organosiloxane copolymer comprising the steps of the following (I) ~ (V): (I) forming a mixture of the following (A) ~ (C): (A) the following organohydrogen siloxane having an average structural _{formula: R 3 Si [OSi (CH} 3) 2] a [OSiH (CH 3)] b OSiR 3 ( here, R represents 1 to 10 carbon atoms of aliphatic unsaturation
A has an average value of 1 to 192, b
Has an average value of 1 to 30. (B) a polyoxyalkylene selected from the group consisting of the following (i) to (iii): (Where (OCH ₂ CH ₂ ) unit and (OCH ₂ CH
(CH ₃ )) units may be block or random, R ¹ is an alkenyl group, R ² may be any substitution that does not interfere with this process, z takes on a value from 1 to 20,
w takes a value of 1 to 20. (C) a solvent ; (II) the mixture in an inert gas at a temperature not exceeding the temperature at which the organohydrogensiloxane reacts with the solvent.
Heating; (III) to the heated mixture, adding a catalytic amount of a noble metal hydrosilation catalyst; (IV) keeping the mixture to a temperature below 130 ℃; (V) recovering said copolymer, wherein the solvent Is the monocarboxylic acid ester of alkanediol
A method characterized in that: 2. The temperature of step (IV) is from 85 ° C. to 130 ° C.
The method of claim 1, wherein the temperature is ° C.